WO2009056447A1

WO2009056447A1 - Washing or cleaning agent in liquid form containing bleaching agent

Info

Publication number: WO2009056447A1
Application number: PCT/EP2008/063878
Authority: WO
Inventors: Sören HÖLSKEN; Peter Schmiedel
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2007-10-30
Filing date: 2008-10-15
Publication date: 2009-05-07
Also published as: DE102007052206A1

Abstract

The invention relates to an aqueous liquid washing or cleaning agent containing tensides and bleaching agent, comprising particulate peroxocarbolic acid and containing methane sulfonic acid or a methane sulfonic acid salt.

Description

"Bleach-containing washing or cleaning agent in liquid form"

The present patent application relates to hydrous liquid detergents or cleaners which contain peroxycarboxylic acid particles.

In detergents and cleaners in liquid form, especially if they contain water but also if they are anhydrous, it may due to chemical incompatibility of the individual ingredients to negative interactions of these ingredients with each other and to decrease their activity and thus decrease the washing performance of the agent as a whole come, even if it is stored relatively short. This decrease in activity relates in principle to all detergent ingredients which carry out chemical reactions in the washing process in order to contribute to the washing result, in particular bleaches and enzymes, although surfactant or sequestering ingredients which are responsible for solution processes or complexing steps, especially in the presence of said chemically reactive ingredients in liquid , in particular aqueous systems are not unlimited shelf life.

The phthalimidoperoxoalkanoic acids, such as 6-phthalimidoperoxohexanoic acid (PAP) are highly efficient bleaches, but are chemically very unstable in conventional liquid detergent formulations. In most cases, they completely decompose in a few days. Even if these liquid agents are freed from possible reactants of the peroxycarboxylic acid, such as unsaturated compounds, aldehydes, amines, chloride, etc., they still decompose in the presence of the surfactants, even if they are not oxidatively attacked. The reason for this may be that although the phthalimidoperoxoalkanoic acids are stable as only slightly water-soluble solids, they dissolve in the presence of surfactants, are highly reactive in this form and dissolve in solution both via a bimolecular reaction with the elimination of singlet oxygen and through Hydrolysis to the Phthalimidoalkansäure and H ₂ O ₂ decompose. The latter is especially true at low washing temperatures and in the occurring Kon- However, concentrations are practically not bleach active, so that in total the bleaching effect of the agent is lost during storage.

It has been proposed on various occasions to solve the problem of the lack of stability of peroxycarboxylic acids in aqueous surfactant-containing liquid detergents by adjusting the solubility of both the peroxycarboxylic acid and the surfactant by setting a high electrolyte concentration (for example up to 30% Na sulfate in the liquid detergent) minimizes as much as possible. The systems thereby become microscopically biphasic, with a typically liquid-crystalline surfactant-rich phase being dispersed in a nearly surfactant-free continuous aqueous phase. By this measure, the dissolution of solid peroxycarboxylic acids can be greatly slowed down, whereby the decomposition rate decreases.

A problem with such formulations with, for example, sodium sulfate, however, is the lack of phase stability and the lack of storage stability, especially under climatic changing conditions. Under alternating climate, the solubility of the sodium sulfate changes very strongly, which can lead to precipitation and the growth of partially very large sulfate crystals in the liquid agents. In addition, the flow behavior of these agents is unsatisfactory and the preparation is complicated in practice, since even during the manufacturing process due to the hydrate formation of the sodium sulfate initially large crystals can form, which do not dissolve again in the thickened formulation.

Another approach to stabilize the bleaching agent is to coat it. For example, European Patent EP 0 510 761 B1 describes a coated bleach granulate. However, it has been found that the application of coating materials by no means always leads to an increase in the stability of the PAP in particular. Often, coating, even with chemically inert materials such as paraffin, even destabilizes the PAP. A coating that should be soluble in the application of the agent, usually in a water-containing product not completely diffusion-tight against water. Thus, although such a coating may possibly suppress the dissolution of the PAP, it does not suppress its hydrolysis to H ₂ O ₂ . In order to solve the problem, it has also been proposed on various occasions not to incorporate all ingredients desirable for a good washing or cleaning result into a liquid agent at the same time, but to provide the user of the composition with several components that he or she only shortly before or during the washing - Or cleaning process together and contain the only mutually compatible ingredients, which come together under the conditions of use used. The common dosing of several components is compared to dosing only a single liquid agent, however, often perceived by the user to be too expensive.

There is therefore still the problem of providing a storage-stable liquid agent, which also contains as many as possible, even incompatible with each other, necessary for a good washing or cleaning result ingredients.

The present invention, which aims to contribute to this, is an aqueous surfactant and bleach-containing liquid washing or cleaning agent which has a particulate peroxocarboxylic acid and is characterized in that it is methanesulfonic acid and / or an alkali metal, alkaline earth metal or ammonium salt of methanesulfonic acid. Among these, preferred are the sodium, potassium, lithium, magnesium and NR ₄ ⁺ salts, each of which R independently of the others being hydrogen, a C 1-8 -alkyl group, a C 2-4 -hydroxyalkyl group or a - ( CH ₂ CH ₂ O) _n H group with n = 2 to 10.

Methanesulfonic acid or one or more of its salts may or may be present in agents according to the invention, if desired, in amounts of up to 30% by weight. Preferably, amounts in the range of 1 wt .-% to 15 wt .-%, in particular in the range of 4 wt .-% to 12 wt .-%. If desired, it is also possible to use magnesium sulfate, sodium sulfate, potassium sulfate or any desired mixture of these; amounts in the range of 1 wt .-% to 15 wt .-%, in particular in the range of 4 wt .-% to 12 wt .-% are preferred. In a preferred embodiment, the agent contains 2 wt .-% to 15 wt .-%, in particular 4 wt .-% to 12 wt .-% of a mixture of alkali metal methanesulfonate and alkali metal sulfate, with sodium being the most preferred alkali metal.

The pH of compositions according to the invention is preferably in the range from 2 to 7, in particular between 3 and 6 and particularly preferably between 3.5 and 5. Water may in inventive compositions, if desired, in amounts of up to 90 wt .-%, in particular 20 wt. -% to 75 wt .-%, be included; if necessary, however, these areas can also be exceeded or fallen short of.

The content of peroxycarboxylic acid in the inventive compositions is preferably 0.5% by weight to 25% by weight, in particular 1% by weight to 20% by weight and particularly preferably 1.5% by weight to 15% by weight. -%. If the peroxycarboxylic acid is not in solid form at room temperature, it may have been formulated in a known manner using inert carrier materials in particulate form; However, a peroxycarboxylic acid which is solid at room temperature is preferably used in optionally coated form. The peroxycarboxylic acid, which may also be referred to as organic peracid, may carry aliphatic and / or cyclic, including heterocyclic and / or aromatic, radicals. There are, for example, peroxo formic acid, peroxoacetic acid, peroxopropionic acid, peroxohexanoic acid, peroxobenzoic acid and their substituted derivatives such as m-chloroperoxobenzoic acid, the mono- or di-peroxophthalic acids, 1,12-diperoxododecane diacid, nonylamidoperoxoadipic acid, 6-hydroxyperoxohexanoic acid, the phthalimidoperoxycarboxylic acids such as 4- Phthalimidoperoxobutanoic acid, 5-phthalimidoperopentanoic acid, 6-phthalimidoperoxohexanoic acid and 7-phthalimidoperoxoheptanoic acid, N, N'-terephthaloyl-di-6-aminoperoxohexanoic acid and mixtures of these. Preferred peracids include the phthalimidoperoxoalkanoic acids, especially 6-phthalimidoperoxohexanoic acid (PAP).

If desired, the peroxycarbonic acid particles contained in the agent according to the invention may be coated. It is important that the coating material dissolves as little as possible in the liquid medium surrounding the coated peroxycarboxylic acid particles, but under the conditions of use of the composition (at a higher temperature, pH value changing by dilution with water, or the like), the coated peroxo carboxylic acid releases. Preferred coating materials include those which consist, at least in part, of saturated fatty acid and / or paraffin. The chain length of the fatty acid is preferably greater than C ₁₂ , particularly preferred is stearic acid. Paraffin wax is generally a complex mixture without a sharp melting point. For characterization is usually determined its melting range by differential thermal analysis (DTA), and / or its solidification point. This is the temperature at which molten material passes from the liquid to the solid state by slow cooling. Preferably, waxes are used, which solidify in the range of 20 ⁰ C to 70 ⁰ C. It should be noted that even at room temperature appearing paraffin wax mixtures may contain different proportions of liquid paraffin. Particularly preferred paraffin wax mixtures have at 40 ^° C. a liquid fraction of at least 50% by weight, in particular from 55% by weight to 80% by weight, and at 60 ^° C. a liquid fraction of at least 90% by weight. It is also preferred if the paraffins contain the lowest possible volatile components. Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 110 ⁰ C and atmospheric pressure vaporizable fractions. Particularly preferred paraffin waxes include those which melt in the range from 40 ^° C. to 65 ^° C., in particular from above 50 ^° C. to 60 ^° C. It has been found that, especially at low pH values, the stability of PAP in the agents according to the invention is very good, so that a coating is unnecessary for stabilizing the PAP. However, a coating of the peroxycarboxylic acid can contribute to the increased stability of enzymes when they are contained in an agent according to the invention. In particular, in the presence of enzymes, therefore, a PAP coating is advantageous.

A coating material, if present, is preferably applied to the particulate peroxycarboxylic acid in amounts such that the coated peroxycarboxylic acid particles consist of 1% to 50% by weight of the coating material. The diameters of the coated Peroxocarbonsäureteilchen are preferably in the range of 100 microns to 3000 microns, in particular in the range of 1500 microns to 2500 microns; Therefore, it starts from correspondingly finely divided Peroxocarbonsäurematerial and covers it with the wrapping material. In addition to water, surfactant, methanesulfonic acid or derem salt and the optionally coated Peroxocarbonsäureteilchen a liquid detergent or cleaning agent according to the invention all conventional ingredients in such agents, such as solvents, builders, enzymes and other auxiliaries such as soil repellants, thickeners, dyes and fragrances or contain similar.

In a preferred embodiment, it contains nonionic surfactants and / or organic solvents and optionally anionic surfactants, cationic surfactants and / or amphoteric surfactants.

Surfactants of the sulfonate type, alk (en) ylsulfates, alkoxylated alk (en) ylsulfates, ester sulfonates and / or soaps are preferably used as anionic surfactants.

Surfactants of the sulfonate type are preferably C9-Ci3 alkyl benzene sulfonates, Olefϊnsulfonate, ie mixtures of alkene and hydroxyalkane sulfonates and disulfo naten how to ₈ monoolefins with terminal or internal double bond by sulfonation with gaseous, for example, from C ₂ -C Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.

Alk (en) yl sulfates are the alkali and especially the sodium salts of Schwefelsäurehalbester the Cio-CI8 fatty alcohols, for example, from coconut fatty alcohol, Talgfettalko- be alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C8-C ₂ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis. For washing-technical interest, C 12 -C 13 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and C 14 -C 15 -alkyl sulfates and C 14 -C 16 -alkyl sulfates are particularly preferred. 2,3-alkyl sulfates, which can be obtained, for example, as commercial products of the Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also, the sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C7-C21 alcohols, such as 2-methyl branched C9-C11 alcohols 7 average of 3.5 moles of ethylene oxide (EO) or Ci2-Ci8 fatty alcohols with 1 to 4 EO, are suitable. Due to their high foaming behavior, they are usually used in detergents only in relatively small amounts, for example in amounts of from 0 to 5% by weight.

Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

As further anionic surfactants are particularly soaps into consideration. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, for. As coconut, palm kernel or Taigfettsäuren, derived soap mixtures. In particular, those soap mixtures are preferred which are composed of 50 to 100 wt .-% of saturated Ci ₂ -C ₂₄ fatty acid soaps and 0 to 50 wt .-% of oleic acid soap.

Another class of anionic surfactants is the class of ether carboxylic acids obtainable by reacting fatty alcohol ethoxylates with sodium chloroacetate in the presence of basic catalysts. They have the general formula: RO- (CH ₂ -CH ₂ -O) _P -CH ₂ -COOH with R = C ₁ -C ₁₈ and p = 0.1 to 20. Ethercarboxylic acids are water-hindered and have excellent surfactant properties.

Cationic surfactants contain the surface activity of the high molecular weight hydrophobic residue upon dissociation in aqueous solution in the cation. The most important representatives of cationic surfactants are the quaternary ammonium compounds of the general formula: (R ¹ R ² R ³ R ⁴ N ⁺ ) XT. Here, R ^{1 is} C ¹ -C ₈ -alk (en) yl, R ² to R ^4, independently of one another, are C _n H _{2n + I p X} - (Y ¹ (CO) R ⁵ ) _P - (Y ² H) _X , where n stands for integers without 0 and p and x stand for integers or 0. Y ¹ and Y ² are each independently O, N or NH. R ⁵ denotes a C ₃ -C ₂₃ -alk (en) yl chain. X is a counterion, which is preferably selected from the group of alkyl sulfates and alkyl carbonates. Particularly preferred are cationic surfactants in which the nitrogen group is substituted by two long acyl and two short alk (en) yl radicals. 8th

Amphoteric or ampholytic surfactants have a plurality of functional groups which can ionize in aqueous solution and, depending on conditions of the medium, impart anionic or cationic character to the compounds. Near the isoelectric point, the amphoteric surfactants form internal salts, rendering them difficult or insoluble in water. Amphoteric surfactants are subdivided into ampholytes and betaines, the latter being present in solution as zwitterions. Ampholytes are amphoteric electrolytes, ie compounds which possess both acidic and basic hydrophilic groups and thus behave acidic or basic depending on the condition. Betaines are compounds with the atomic grouping R ₃ N ⁺ -CH ₂ -COO ^" , which show typical properties of zwitterions.

The nonionic surfactants used are preferably alkoxylated and / or propoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per mole of alcohol. Particularly preferred are Cs-Cioè-alcohol alkoxylates, advantageously ethosulfate xylierte and / or propoxylated Cio-Cis-alcohol alkoxylates, in particular C ₂ -C ₄ holalkoxylate -Aiko-, with a degree of ethoxylation from 2 to 10, preferably between 3 and 8, and / or a degree of propoxylation between 1 and 6, preferably between 1.5 and 5. The stated degrees of ethoxylation and propoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow ranges ethoxylates / propoxylates, NRE / NRP). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (TaIg) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x , z. B. as compounds, especially with anionic surfactants are used, in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol that represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicating partition of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.1 to 1.4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester. Particularly preferred are C ₁₂ -C ₁₈ fatty acid methyl esters having an average of 3 to 15 EO, in particular having an average of 5 to 12 EO.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer." This spacer is usually a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart to act independently of one another generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water, but in exceptional cases the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer tris sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are particularly characterized by their bi- and multifunctionality. Thus, the end-capped surfactants mentioned have good network properties. 10 properties and are low-foaming, making them particularly suitable for use in machine washing or cleaning processes. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides.

The amount of surfactants present in the agents according to the invention is preferably 0.1% by weight to 50% by weight, in particular 10% by weight to 40% by weight, and particularly preferably 20% by weight to 70% by weight. -%. Preferably, only mixtures of anionic and nonionic surfactants are used.

Polydiols, ethers, alcohols, ketones, amides and / or esters, in amounts of from 0 to 90% by weight, preferably 0.1 to 70% by weight, in particular 0.1 to 60% by weight, may preferably be used as organic solvents. %, in each case based on the amount of water available. Preference is given to low molecular weight polar substances, such as, for example, methanol, ethanol, propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, dipropylene glycol monomethyl ether and dimethylformamide or mixtures thereof.

Particularly suitable enzymes are those from the class of hydrohalases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrogels, and mixtures of said enzymes. All of these hydro lases contribute to the removal of stains such as proteinaceous, fatty or starchy stains, and graying in the laundry. Cellulases and other glycosyl hydro- lases can contribute to color retention and to increasing the softness of the textile by removing pilling and micro-goggles. Oxidoreductases can also be used to enhance the bleaching or to inhibit the transfer of color.

Particularly suitable are enzymatic active substances obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. Enzyme mixtures, for example from protease and amylase or protease and lipase or 11 lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing Mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, CC amylases, iso-amylases, pullulanases and pectinases. Cellulases used are preferably cellobiohydrolases, endoglucanases and β-glucosides, which are also cellobiases, or mixtures thereof. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.

The proportion of enzymes or enzyme mixtures may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 3 wt .-%. They are preferably formulated in particulate form in agents according to the invention and used, if appropriate, coated.

Examples of further detergent ingredients which may be present include builders, cobuilders, soil repellents, alkaline salts and also foam inhibitors, complexing agents, corrosion inhibitors, enzyme stabilizers, grayness inhibitors, optical brighteners and UV absorbers.

Organic builders useful as builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. 12

The acids themselves can also be used. In addition to their building action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here. Further useable acidulants are known pH regulators, such as sodium bicarbonate and sodium hydrogen sulfate.

Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group.

Suitable polymers may also include substances consisting partly or wholly of units of vinyl alcohol or its derivatives. 13

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol. The (co) polymeric polycarboxylates can be used either as an aqueous solution or, preferably, as a powder.

To improve the water-solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives. Further preferred copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500 000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular 14 is from 2 to 30, where DE is a common measure of the reducing effect of a polysaccharide as compared to dextrose which has a DE of 100. Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also yellow dextrins and white dextrins with relatively high molecular weights in the range from 2 000 to 30 000 g / mol can be used. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this connection are glycerol disuccinates and glycerol tri-succinates. Suitable amounts are, in particular, in zeolite-containing and / or silicon-containing formulations at 3 to 15 wt .-%. Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

In addition, the compositions may also contain components which positively influence the oil and grease washability from textiles, so-called soil repellents. This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component. Examples of preferred oil and fat dissolving components include nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether, as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or 15 nonionic modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

When used in automatic washing processes, it may be advantageous to add conventional foam inhibitors to the compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci ₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with micro-fine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicones, paraffins or waxes.

As complexing agents or as stabilizers in particular for enzymes that are sensitive to heavy metal ions, the salts of polyphosphonic come into consideration. Here, the sodium salts of, for example, l-hydroxyethane-1,1-diphosphonate, but also diethylenetriaminepentamethylenephosphonate or ethylenediamine tetramethylenephosphonate in amounts of from 0.1% by weight to 5% by weight of the composition are preferably used. Nitrogen-free complexing agents are preferred.

Grayness inhibitors have the task to keep suspended from the fiber debris suspended in the fleet and so prevent the re-raising of the dirt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of (co) polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, for. Degraded starch, aldehyde levels, etc. Also, polyvinylpyrrolidone is useful. However, preference is given to cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and also polyvinyl chloride. 16 pyrrolidone, for example, in amounts of 0.1 to 5 wt .-%, based on the means used.

The funds can optical brighteners such. B. derivatives of Diaminostilbendisulfonsäure or their alkali metal salts. Suitable z. B. salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure, instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl). This class of optical brighteners is preferred. Mixtures of the aforementioned brightener can be used.

In addition, UV absorbers can also be used. These are compounds with pronounced absorption capacity for ultraviolet radiation, which contribute as light stabilizers (UV stabilizers) both to improving the light resistance of dyes and pigments and textile fibers and also protect the skin of the wearer of textile products from UV radiation that is urgently required by the textile , In general, the compounds which are active by radiationless deactivation are derivatives of benzophenone whose substituents, such as hydroxyl and / or alkoxy groups, are usually in the 2- and / or 4-position. Furthermore, substituted benzotriazoles are also suitable, furthermore in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic nickel complexes and natural products such as umbelliferone and the body's own urocanic acid. In a preferred embodiment, the UV absorbers absorb UV-A and UV-B radiation and optionally UV-C radiation and radiate back with wavelengths of blue light, so that they additionally have the effect of an optical brightener. Preferred UV absorbers are triazine derivatives, e.g. B. hydroxyaryl-1,3,5-triazine, sulfonated 1,3,5-triazine, o-hydroxyphenylbenzotriazole and 2-aryl-2H-benzotriazole and bis (anilinotriazinylamino) stilbenedisulfonic acid and derivatives thereof. When 17

UV absorbers can also be used to absorb ultraviolet radiation pigments such as titanium dioxide.

The agents may, if desired, further conventional thickeners and anti-settling agents and viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized and / or ethoxylated hexamethylenediamines and any mixtures thereof contain. Preferred compositions have in measurements with a Brookfϊeld viscometer at a temperature of 20 ⁰ C and a shear rate of 20 min ^"1, a viscosity of 100 to 10,000 mPa-s. The agents may further typical detergents and detergent ingredients such as perfumes and / or dyestuffs, preference being given to those dyestuffs which have no or negligible coloring action on the textiles to be washed .. Preferred quantitative ranges of the totality of the dyestuffs used are less than 1% by weight, preferably less than 0.1% by weight, based on The agent may optionally also contain white pigments such as TiO ₂ .

Preferred agents have densities of 0.5 to 2.0 g / cm ³ , in particular 0.7 to 1.5 g / cm ³ , on. The density difference between the Peroxocarbonsäureteilchen and the liquid phase of the composition is preferably not more than 10% of the density of one of the two and in particular so low that the Peroxocarbonsäureteilchen and preferably also optionally other suspended in the funds solid particles float in the liquid phase.

18

Examples

The chemical stability of an aqueous surfactant-containing agent El, which contained 2.5 wt .-% of a PAP granules and 7% sodium sulfate and 4% sodium methanesulfonate, and that of an agent Vl, which was otherwise the same composition, but which lacked the sodium methanesulfonate (replaced by water) were determined by storing the formulation according to the invention El and the agent Vl at 35 ° C and then their content of PAP in% based on the initial value by iodometric titration at a temperature of 0 ⁰ C were determined.

The following PAP contents were found:

La ^ currently (weeks) 0 4 6

El 100 72, 5 67 8

Vl 100 64, 8 52 9

It can be seen that the stability of the bleaching agent can be considerably increased by the addition of sodium methanesulfonate.

Claims

19 claims

1. Aqueous surfactant and bleach-containing liquid detergent or cleaning agent having a particulate peroxycarboxylic acid, characterized in that it contains methanesulfonic acid and / or an alkali, alkaline earth or ammonium salt of methanesulfonic acid.

2. Composition according to claim 1, characterized in that it contains 0.5 wt .-% to 25 wt .-%, in particular 1 wt .-% to 20 wt .-% peroxocarboxylic acid.

3. Composition according to claim 1 or 2, characterized in that it contains a solid at room temperature peroxocarboxylic acid in optionally coated form.

4. Composition according to one of claims 1 to 3, characterized in that the peroxycarboxylic acid is a Phthalimidoperoxoalkansäure, in particular 6-Phthalimido- peroxohexansäure (PAP).

5. Composition according to one of claims 1 to 4, characterized in that it contains up to 30 wt .-% of methanesulfonic acid or one or more of their salts.

6. Composition according to one of claims 1 to 5, characterized in that it contains 1 wt .-% to 15 wt .-%, in particular 4 wt .-% to 12 wt .-% methanesulfonic acid or one or more of its salts.

7. Composition according to one of claims 1 to 6, characterized in that it is 0.1

Wt .-% to 50 wt .-%, in particular 10 wt .-% to 40 wt .-% surfactant.

8. Composition according to one of claims 1 to 7, characterized in that it contains a mixture of anionic and nonionic surfactants. 20

9. Composition according to one of claims 1 to 8, characterized in that it has a pH in the range of 2 to 7, in particular between 3 and 6.

10. Composition according to one of claims 1 to 9, characterized in that the densities of the optionally coated Peroxocarbonsäureteilchen and the liquid phase of the agent differ by not more than 10% from each other.